Tetrabenzochrysene derivatives and method for manufacturing the same

Abstract

To provide a simple method for synthesizing a tetrabenzochrysene derivative without using a cross-coupling method using heavy metals, and to provide a novel tetrabenzochrysene derivative.SOLUTION: There is provided a method for synthesizing a tetrabenzochrysene derivative, including the steps of: (a) dimerizing a benzofluorenone derivative to produce a spiroketone derivative; (b) reducing the carbonyl group of the obtained spiroketone derivative to produce a spiroalcohol derivative having a hydroxyl group; and (c) dehydrating the obtained spiroalcohol derivative to obtain the tetrabenzochrysene derivative.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a tetrabenzochrysene derivative and a method for producing the same. [Background technology]

[0002] Tetrabenzochrysene is a promising organic compound as a highly functional material. The most notable feature of the tetrabenzochrysene structure is its highly non-planar pi-conjugated structure, which has attracted the attention of many researchers. Here, non-planarity means that the pi-conjugated aromatic group is twisted in a helical shape, and the helical structure is expected to be used as a hole transport material in thin-film transistors and as a light-emitting element in organic light-emitting diodes. It has high potential value in terms of photoquantum properties (quantum yield and excitation lifetime), electronic properties, and heat resistance, and attempts are being made to incorporate it into polymer materials, etc. In addition, tetrabenzochrysene has a high refractive index and is expected to be used as an optical material for plastic lenses, etc.

[0003] However, it is known that the synthesis of polycyclic aromatic hydrocarbons such as tetrabenzochrysene becomes more difficult as the number of aromatic rings increases. Metal reagents are often effective in synthesizing such polycyclic aromatic hydrocarbons. For example, in Non-Patent Document 1, hexacyclic dibenzochrysene is prepared by making full use of a method using a palladium reagent. In Non-Patent Document 2, a method using a palladium reagent is also used to increase the number of rings at once by attempting to extend the condensed rings in three directions by [2+2+2] cyclization of benzyne. However, there is a concern that such heavy metal reagents remain in the final product and may reduce the functionality of the material or product. In addition, heavy metal reagents are expensive and difficult to handle, which causes a problem of reduced productivity. [Prior art documents] [Non-patent literature]

[0004] [Non-Patent Document 1] W. Matsuoka, et al, Angew.Chem.Int.Ed.2017,56,12224-12228 [Non-Patent Document 2] Pena, et al, Acc.Chem.Res.2019,52,2472-2481) Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present invention is to provide a simple method for synthesizing a tetrabenzochrysene derivative without using a cross-coupling method using a heavy metal, as well as to provide a novel tetrabenzochrysene derivative. [Means for solving the problem]

[0006] The present inventors have further investigated a method for synthesizing a tetrabenzochrysene derivative and have found that a tetrabenzochrysene derivative can be synthesized without using a cross-coupling method using heavy metals by dimerizing benzofluorenone (11H-benzo[b]fluoren-11-one) in a triisopropyl phosphite solvent, followed by a reduction reaction and a cation rearrangement reaction, thereby completing the present invention.

[0007] That is, the present invention (1) is (a) dimerizing a benzofluorenone derivative to produce a spiroketone derivative; (b) reducing the carbonyl group of the resulting spiroketone derivative to produce a spiroalcohol derivative having a hydroxyl group; and (c) Dehydrating the resulting spiro alcohol derivative to obtain a tetrabenzochrysene derivative. The present invention relates to a method for producing a tetrabenzochrysene derivative comprising the steps of:

[0008] The present invention (2) relates to the spiro ketone derivative represented by the following formula: [ka] ,or, [ka] wherein the spiro alcohol derivative is a compound represented by the following formula: [ka] ,or, [ka] The present invention relates to a method for producing a tetrabenzochrysene derivative according to the present invention (1), which is a compound represented by the following formula:

[0009] The present invention (3) relates to a tetrabenzochrysene derivative represented by the following formula: [ka] ,or, [ka] The present invention relates to a method for producing a tetrabenzochrysene derivative according to the present invention (1) or (2), which is a compound represented by the following formula:

[0010] The present invention (4) is a method for producing a tetrabenzochrysene derivative according to any one of the present inventions (1) to (3), in which in the step (a) of producing a spiroketone derivative, dimerization of a benzofluorenone derivative is carried out in the presence of a trialkyl phosphite.

[0011] The present invention (5) is The following formula [ka] It is a tetrabenzochrysene derivative represented by the formula:

[0012] The present invention (6) is The following formula [ka] ,or, [ka] It is a spiroketone derivative represented by the formula:

[0013] The present invention (7) is The following formula [ka] ,or, [ka] It is a spiro alcohol derivative represented by the formula: Effect of the Invention

[0014] According to the method for producing a tetrabenzochrysene derivative of the present invention, a novel tetrabenzochrysene derivative can be synthesized, and the tetrabenzochrysene derivative can be easily synthesized without using a cross-coupling method using a heavy metal. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] The method for producing the tetrabenzochrysene derivative of the present invention comprises the steps of: (a) dimerizing a benzofluorenone derivative to produce a spiroketone derivative; (b) reducing the carbonyl group of the resulting spiroketone derivative to produce a spiroalcohol derivative having a hydroxyl group; and (c) Dehydrating the resulting spiro alcohol derivative to obtain a tetrabenzochrysene derivative. The chemical reaction formula of the production method of the present invention is shown below.

[0016] [ka]

[0017] (a) Dimerization of benzofluorenone derivatives The starting material benzofluorenone (11H-benzo[b]fluoren-11-one) may have a substituent, such as an alkyl group, an allyl group, an aryl group, an alkenyl group, an alkynyl group, a halogeno group, a hydroxyl group, an alkyl ether group, a polyoxyalkylene group, an amide group, or an amino group.

[0018] The method of dimerizing the benzofluorenone derivative is not particularly limited, and a preferred method is a method carried out in the presence of a Lewis base reagent having high oxygen affinity, such as trialkyl phosphite. The amount of the activation reagent, such as trialkyl phosphite, is preferably 2 equivalents or more. The reaction temperature is not particularly limited, and is preferably 90 to 200°C, more preferably 160 to 190°C. Among the trialkyl phosphites, triisopropyl phosphite is preferred in terms of reaction yield.

[0019] When benzofluorenone, which does not have a substituent on the aromatic ring, is used as a starting material and is dimerized, the following formula is obtained: [ka] ,or, [ka] A spiroketone derivative represented by the formula (1) can be obtained. Two isomers are generated by dimerization of benzofluorenone. One of the compounds can be separated and purified and subjected to the reduction reaction of the spiroketone derivative (b). The method of separation and purification is not particularly limited, and examples thereof include recrystallization and column chromatography.

[0020] (b) Reduction reaction of spiroketone derivatives The method for reducing the spiroketone derivative obtained by dimerizing the benzofluorenone derivative is not particularly limited, and examples thereof include catalytic reduction using a reducing agent such as sodium borohydride or lithium aluminum hydride, or hydrogen (gas).

[0021] The spiroketone derivative is reduced to give the following formula: [ka] ,or, [ka] When the spiroketone derivatives are separated and purified, and one of the spiroketone derivatives is used, only the corresponding spiroalcohol derivative is produced.

[0022] (c) Dehydration reaction of spiro alcohol derivatives The method for dehydrating the spiro alcohol derivative is not particularly limited, but it is preferably carried out in the presence of a catalyst such as ethylaluminum dichloride, aluminum trichloride, iron trichloride, (zero-valent) iron, concentrated hydrochloric acid, hydrochloric acid, acetic acid, trifluoroacetic acid, dilute sulfuric acid, methanesulfonic acid, paratoluenesulfonic acid, benzenesulfonic acid, acetic acid, or trifluoromethanesulfonic acid.

[0023] When the spiro alcohol derivative is dehydrated, the compound of the formula [ka] ,or, [ka] It is possible to obtain a tetrabenzochrysene derivative represented by the following formula: When one of the spiro alcohol derivatives is used as the spiro alcohol derivative, the corresponding tetrabenzochrysene derivative is obtained as the main product. When a mixture of two tetrabenzochrysene derivatives is obtained, they can be separated and purified by a method such as recrystallization or column chromatography.

[0024] The tetrabenzochrysene derivatives, spiroketone derivatives, and spiroalcohol derivatives of the present invention are applicable in the fields of polymer materials, high heat-resistant resins, optical functional materials, organic electronics materials, and chemical sensor materials. Specifically, they can be used as low transmission loss substrate materials, raw materials for low dielectric and optically adhesive polyimide resins, materials for lithography, resist materials, materials for organic EL, resin materials such as adhesives, materials for super engineering plastics, materials for organic semiconductors, materials for organic solar cells, and flexible printed circuit boards. In particular, they can be used as hole transport materials for thin film transistors, light-emitting elements for organic light-emitting diodes, and precursor compounds thereof. In addition, they have a high refractive index and can be used as optical materials for plastic lenses, etc. EXAMPLES

[0025] Examples of the present invention will be described below, but the present invention is not limited to the following examples.

[0026] In the examples, reactions were carried out under an argon or nitrogen atmosphere, and experiments were carried out under water-free conditions unless otherwise specified. Purchased anhydrous solvents and reagents were used without further purification to improve purity. Thin-layer chromatography was performed using Merck silica 60F. 254 The column chromatography was performed using silica gel 60N (Kanto Chemical Co., Ltd.) For high-resolution mass measurement (HRMS), either time-of-flight mass spectrometry (MALDI-TOF or LCMS-IT-TOF) or direct mass spectrometry (DART-MS) was used.

[0027] 1 H-NMR, 13 The C-NMR spectra were measured at 400 MHz and 100 MHz using a 5 mm QNP probe. Chemical shift values ​​are shown in δ (ppm), and the reference values ​​in each solvent are 1 H-NMR: CHCl3 (7.26), CH2Cl2 (5.32), DMSO (2.50); 13C-NMR: CDCl3 (77.0), DMSO (39.5). Splitting patterns are indicated as s: singlet, d: doublet, t: triplet, q: quartet, m: multiplet, br: broad line.

[0028] According to the scheme shown below, the desired tetrabenzochrysene 1 and 2 were prepared using spiroketone 3 / iso-3 and spiroalcohol 4 / iso-4 as synthetic intermediates. The spiroketone and spiroalcohol were obtained as isomeric mixtures. On the other hand, the mixture of tetrabenzochrysene 1 and 2 was recrystallized in chloroform, and only tetrabenzochrysene 1 was precipitated as a pure product. The residue was purified using a column to obtain tetrabenzochrysene 2. [ka]

[0029] Example 1 Synthesis of spiroketone 3 / iso-3 isomeric mixture 11H-benzo[b]fluoren-11-one (13 g, 58 mmol) and triisopropyl phosphite (33 mL, 150 mmol) were added to a one-neck flask under atmospheric pressure. The mixture was stirred at 170°C for 64 hours to confirm the progress of the target reaction, and then cooled to 60°C. Distilled water was slowly added dropwise, and the temperature was raised again to 80°C. After stirring for 2 hours, the temperature was naturally lowered to room temperature and diluted with toluene. The organic layer was separated, and the aqueous layer was extracted with toluene. The combined organic layer was washed with saturated saline, dried with Glauber's salt, concentrated to remove the solvent, dried in vacuum, and purified using a filtration column using silica gel, obtaining 9.4 g of a crude product. Further, silica gel column purification was performed to obtain 6.8 g (53%) of an isomer mixture as a yellow solid. The isomer ratio was 52:48.

[0030] Analytical data for Spiroketone 3 / iso-3 1HNMR(400MHz, CDCl3)8.65(s,1H),8.62(s,1H),8.56(s,1H),8.45(d,J=8.0Hz,1H),8.30(d,J=8.2Hz,1 H),8.25(s,1H),8.22(s,1H),8.08-7.85(m,9H),7.69-7.08(m,23H),6.71(dd,J=7.9Hz,1.3Hz,1H)ppm; 13 CNMR(100MHz, CDCl3)197.3(C=O),197.2(C=O),148.0,147.9,145.71,145.65,141.3,141.2,139.9,139.83,139.80,1 38.6,137.7,137.0,135.2,134.1,134.0,133.8,133.6,133.1,132.7,131.3,130.7,130.2,129.4,129.1,128.7(many peaks are overlapped),127.9,127.4,127.2,126.9,126.5,126.00,125.97,125.7,125. 6,124.6,124.5,124.4,124.3,124.0,122.8,121.5,121.4,119.25,119.20ppm; MS (DART-TOF) m / z: 445 [MH] + ; IR(neat)3051,1681(C=O),1597,1262,871,759,742,716,472cm -1 ; HRMS (DART-TOF) calculation for C 34 H 21 O:445.1592[MH] + ,found:445.1605.

[0031] Example 2 Synthesis of スピロアルコール4 / iso-4 heterosexual mixture Spiro ketone mixture 3 / iso-3 (7.5 g, 17 mmol, isomer mixture with a molar ratio of 52:48), toluene (8.0 mL), and methanol (1.6 mL) were added to a one-neck flask under atmospheric pressure, and the mixture was heated to 45°C. After stirring the reaction solution for 15 minutes, sodium borohydride (260 mg, 6.8 mmol) was slowly added and stirred for 30 minutes. Acetone was added and stirred for 30 minutes to inactivate the excess reducing agent, and the mixture was allowed to cool naturally to room temperature and diluted with toluene. The organic layer was washed with water, washed with saturated saline, dried with sodium sulfate, concentrated to remove the solvent, and dried in vacuum to obtain 7.6 g of crude product. Column purification using silica gel was performed to obtain 7.0 g (93%) of spiro alcohol as an orange-white solid.

[0032] Analytical data for spiro alcohol 4 / iso-4 1 HNMR(400MHz,CDCl3)8.47-8.46(m,4H),8.41(s,1H),8.27-8.17(m,10H),8.05-7.22(m,59H),7.14-7.03(m,4H),6.94-6.92(m, 1H),6.83(d,J=7.6Hz,2H),6.77(d,J=7.8Hz,2H),6.61(d,J=7.6Hz,1H),5.70(s,1H),5.52(s,1H),5.47(s,1H),5.32(s,1H)ppm; 13CNMR(100MHz,CDCl3)149.1,149.0,147.4,147.2,147.1,146.7,144.6,144.2,142.2,142.0,141.2,141. 0,140.94,140.85,140.6,140.4,140.12,140.06,138.3,138.1,137.9,137.8,135.9,135.8,134.3(many peaks are overlapped),133.8(many peaks are overlapped),132.72,132.68,132.4,129.5,129.4,129.1(many peaks are overlapped),128.7(many peaks are overlapped),128.3,128.2,127.7,127.4,126.8(many peaks are overlapped),126.4(many peaks are overlapped),126.1,126.0,125.9,125.7,125.6,125.33,125.25,125.2,124.9,124.8,124.4,124.2,124.1,124.0.1 23.52,123.45,121.3,121.28,121.25,121.2,118.94,118.90,118.8,76.2,76.1,75.8,75.7,61.74,61.66,61.5ppm; MS(DART-TOF)m / z:429[MH] + ; IR(neat)3562(OH),3418(OH),3052,1499,1435,1214,1017,882,742cm -1 ; HRMS(DART-TOF)calcd.for C 34 H 21 + :429.1638[M-OH] + ,found;429.1660.

[0033] Example 3 Preparation of tetrabenzochrysene 1 and 2 Spiro alcohol mixture 4 / iso-4 (7.0 g, 16 mmol) and toluene (50 mL) were added to a single-neck flask. Methanesulfonic acid (0.01 mL, 0.02 mmol) was added to the reaction solution, and the mixture was heated to reflux at 130°C. After stirring for 30 minutes, the temperature was lowered to 0°C, and saturated sodium bicarbonate water was added. The mixture was filtered under reduced pressure and washed with methanol. After drying under vacuum, 5.8 g of a yellow crude product was obtained (isomer mixture, isomer ratio approximately 50:50). The crude product was recrystallized to obtain tetrabenzochrysene 1 as a yellow single compound in 27% yield (1.8 g) (the structure was confirmed by X-ray crystal structure analysis). The mother liquor residue was then subjected to column purification to obtain tetrabenzochrysene 2 in 10% yield.

[0034] Analytical data for Tetrabenzochrysene 1 Rf value 0.51(hexane / CH2Cl2=2:1); Mp333-335℃; 1 HNMR(400MHz,CDCl3)9.16(s,2H,H-5),9.13(s,2H,H-20),8.86(dd,J=8.0,1.2Hz,2H,H- 6),8.80(dd,J=8.0,1.2Hz,2H,H-9),8.16(dd,J=8.0,1.1Hz,2H,H-4),8.04(dd,J=8.0,1 .1Hz,2H,H-1),7.75(ddd,J=8.0,7.1,1.2Hz,2H,H-7),7.70(ddd,J=8.0,7.1,1.2Hz,2H, H-8),7.59(ddd,J=8.0,7.1,1.1Hz,2H,H-3),7.56(ddd,J=8.0,7.1,1.1Hz,2H,H-2)ppm; 13 CNMR(100MHz,CHCl3)132.4(C-9a),132.0(C-19b),131.9(C-5a),130.3(C-20a),130.2(C-4a),129.1(C-9),128.7(C-1),128.6(C -4),128.5(C-5c),128.4(C-7),127.9(C-8),127.5(C-2),127.3(C-3),126.5(C-20),126.3(C-5),124.6(C-6),122.7(C-5b)ppm; MS(DART-TOF)m / z:429[MH] + ; IR(neat)3043,1492,1219,1128,903,871,732,459cm -1 ; HRMS(DART-TOF)calcd.for C 34 H 21 :429.1643[MH] + ,found;429.1656; Anal.Calcd for C 34 H 20 :C,95.30;H,4.70.Found:C,95.30;H,4.72.

[0035] Analytical data for Tetrabenzochrysene 2 1 HNMR(400MHz,CDCl3)9.30(s,2H,H-20),9.17(s,2H,H-5),8.83(dd,J=8.0,1.3Hz,2H,H-9),8.60(dd,J=8.0, 1.3Hz,2H,H-6),8.17(d,J=7.8Hz,2H,H-4),8.04(d,J=7.8Hz,2H,H-1),8.05-7.56(m,H-2,H-3,H-7,H-8)ppm. [Industrial Applicability]

[0036] The method for producing a tetrabenzochrysene derivative of the present invention is applicable as a method for producing a tetrabenzochrysene derivative useful as a hole transport material for a thin film transistor or a light emitting element for an organic light emitting diode. The tetrabenzochrysene derivative of the present invention is also applicable to a hole transport material for a thin film transistor, a light emitting element for an organic light emitting diode, or a high refractive index material. The tetrabenzochrysene derivative of the present invention is also applicable to the development of a material having chiroptical properties.

[0037] The most important element of the present invention is that tetrabenzochrysene (1) and (2) were synthesized by deriving them from the starting material fluorenone without using any metal reagents.

[0038] Its main effect is, (1) The synthesis route is short, consisting of only three steps, and the method is simple, so it is easy to supply in large quantities. The structure was also determined using X-ray analysis. Our synthesis method does not rely on the cross-coupling method using typical transition metals, so it does not produce waste materials such as heavy metals. (2) Unsubstituted octacyclic polycyclic aromatic hydrocarbons with high carbon density (C 34 H 20 ), a high refractive index can be expected. (3) Because it dissolves in organic solvents, it can also be used for chemical modification and molding.

Claims

1. (a) dimerizing a benzofluorenone derivative to prepare a spiroketone derivative; (b) reducing the carbonyl group of the resulting spiroketone derivative to produce a spiroalcohol derivative having a hydroxyl group; and (c) A step of dehydrating the obtained spiro alcohol derivative to obtain a tetrabenzochrysene derivative. A method for producing a tetrabenzochrysene derivative comprising the steps of:

2. The spiroketone derivative is represented by the following formula: 【Chemistry 1】 ,or, 【Chemistry 2】 wherein the spiro alcohol derivative is a compound represented by the following formula: 【Chemistry 3】 ,or, 【Chemistry 4】 The method for producing the tetrabenzochrysene derivative according to claim 1, wherein the tetrabenzochrysene derivative is a compound represented by the formula:

3. The tetrabenzochrysene derivative is represented by the following formula: 【Chemistry 5】 ,or, 【Chemistry 6】 The method for producing the tetrabenzochrysene derivative according to claim 1 or 2, which is a compound represented by the formula:

4. 3. The method for producing a tetrabenzochrysene derivative according to claim 1 or 2, wherein in the step (a) of producing a spiroketone derivative, the dimerization of the benzofluorenone derivative is carried out in the presence of a trialkyl phosphite.

5. The following formula 【Chemistry 7】 A tetrabenzochrysene derivative represented by the formula:

6. The following formula 【Chemistry 8】 ,or, 【Chemistry 9】 A spiroketone derivative represented by the formula:

7. The following formula 【Chemistry 10】 ,or, 【Chemistry 11】 A spiro alcohol derivative represented by the formula:

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